JPH08334850A - Silver halide photographic emulsion and silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic emulsion and the silver halide color photographic sensitive material high on sensitivity and improved in graininess and further improved in pressure resistance. CONSTITUTION: The silver halide photographic emulsion contains the silver halide grains which comprises flat silver halide grains having an aspect ratio of >=8 and a size distribution of monodispersion and composed many of crystal faces 111} and 100} and >=10 dislocation lines in the fringe part of each grain in >=50% of the projection areas of the total silver halide grains and the silver halide color photographic sensitive material contains this photographic emulsion.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion useful in the field of photography and a silver halide photographic color light-sensitive material using the same. More specifically, it relates to a silver halide photographic emulsion having improved sensitivity, graininess and pressure resistance, and a silver halide color photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art In recent years, performance demands on photographic silver halides have become more and more severe, and demands for improvement in pressure resistance of silver halide photographic light-sensitive materials have been made against photographic characteristics such as high sensitivity and excellent graininess. Even more than ever before.

Various pressures are generally applied to a photographic light-sensitive material coated with a silver halide emulsion. For example, a negative film for general photography is bent or rubbed when it is wound in a cartridge or loaded in a camera, and is also subjected to great pressure during cutting and processing.

As described above, it is generally known that when various pressures are applied to the photographic light-sensitive material, the photographic performance changes, and a photographic material that does not change the photographic performance due to these pressures is used. It is strongly desired to provide.

As a means for improving the pressure characteristics, a method of incorporating a plasticizer such as a polymer or an emulsion or a method of reducing the silver halide / gelatin ratio of a silver halide emulsion is used to reach the pressure. It is known to prevent it. However, at present, it is difficult to achieve a sufficient effect by any of the methods.

In response to the demand for improved pressure characteristics, emulsions composed of core / shell type silver halide grains having a silver iodobromide layer having a high silver iodide content have been actively studied. As an example of high sensitivity and improvement of pressure resistance, an emulsion having a high silver iodide content inside the grain is disclosed in JP-A-59-99433.
JP-A-60-35726, JP-A-60-1477
No. 26 is disclosed in each publication. However, when these examples were additionally tested, the effect of improving pressure resistance was insufficient. Further, in Japanese Patent Laid-Open No. 3-189642,
Graininess is improved and fog is reduced by introducing a dislocation line into the fringe portion of the grain, but the pressure resistance is significantly deteriorated, and the sensitivity is reduced due to the application of pressure after exposure.

Further, in Japanese Patent Laid-Open No. 6-332093, an emulsion having an aspect ratio of 8 or more and containing dislocation lines is used to improve sensitivity and to improve pressure resistance. Accompanied by deterioration. In addition, the higher the aspect ratio, the more unstable the edge part of the particle becomes, and the shape of the hexagonal flat plate is such that a circular flat plate with the melted edge part is mixed, and the performance between particles varies. Was not at a level that could withstand.

Furthermore, European patent EP 0515894A1
In order to achieve high sensitivity and low fog, an emulsion having a {100} plane at the edge of a flat plate with a high aspect ratio of {111} plane as the main plane and being doped with a cyano complex of Group 8 metal However, the graininess was rather deteriorated.

[0009]

In contrast to the above-mentioned problems, the object of the present invention is to improve the above-mentioned problems, to obtain a halogenated compound having high sensitivity, improved graininess, and improved pressure resistance. It is intended to provide a silver photographic emulsion and a silver halide color photographic light-sensitive material.

[0010]

As a result of earnest research, the present inventors have found that the object of the present invention can be achieved by the following.

(1) In a silver halide photographic emulsion containing silver halide grains in a dispersion medium, the grain size distribution of the silver halide grains is monodisperse, and the total projected area of the silver halide grains is 50. % Silver halide grains having an aspect ratio of 8 or more, and mainly {111} and {1
And a tabular silver halide grain consisting of
A silver halide photographic emulsion characterized by having 10 or more dislocation lines per grain in the fringe portion of the grain.

(2) In a silver halide color photographic light-sensitive material having at least one silver halide emulsion on a support, at least one of the silver halide emulsion layers has the silver halide photographic emulsion described in (2) above. A silver halide color photographic light-sensitive material comprising:

The present invention will be described in detail below.

The silver halide photographic emulsion of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chlorobromide, silver chloroiodide, silver chloride and the like as silver halide. Although any of those used for ordinary silver halide emulsions can be used, silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferred.

The silver halide grain according to the present invention may be either a grain whose latent image is mainly formed on the surface or a grain which is mainly formed inside the grain.

The silver halide grains according to the present invention have an aspect ratio (grain diameter / grain thickness ratio) of 8 or more in 50% or more of the total projected area, more preferably 12 or more, further preferably 15 or more. is there. Here, the grain diameter means that when the silver halide grains are observed with a microscope or an electron microscope,
Is the diameter of a circle with an area equal to the projected area of the particle,
Grain thickness is the distance between outer surfaces that are parallel to each other. The particle thickness can be calculated by depositing a metal from the oblique direction of the particle together with the latex for reference, measuring the shadow length of the metal on an electron microscope, and referring to the shadow length of the latex.

The tabular silver halide grains of the present invention occupy 50% or more of the projected area of all silver halide grains, but preferably 60% or more.

The silver halide grains of the present invention are monodisperse emulsions. In the monodisperse emulsion of the present invention, {(standard deviation of grain size distribution) / (average grain size)} × 100 = 20% or less when the breadth of distribution is defined by the breadth of distribution (variation coefficient) [%] And more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, the silver halide grains preferably have two twin planes parallel to each other, and are tabular silver halide grains having two twin planes parallel to the principal plane. It is preferable.

The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide photographic emulsion so that the tabular silver halide grains contained therein are oriented so that their principal planes are parallel to each other on a support. This is cut with a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. The presence of twin planes can be confirmed by observing this section with a transmission electron microscope.

The silver halide grains contained in the silver halide emulsion of the present invention are hexagonal flat plates in shape.

The silver halide grains contained in the silver halide emulsion of the present invention are mainly composed of {111} faces and {100} faces.

In the present invention, the {111} plane and the {1} are mainly used.
Consisting of {00} faces means that the surface of the silver halide grain is {1
11} planes and {100} planes are present, and the ratio of {111} planes to the total surface of the silver halide grain is {1}.
It means that the sum of the proportion of the {00} planes is 60% or more.

In the present invention, it is preferred that 50% or more of the total projected area of silver halide grains have {111} planes and {100} planes on the surface of one silver halide grain.
It is more preferably 60% or more, and most preferably 70% or more.

In the present invention, the ratio of {100} planes of tabular grains is such that {111} planes and {10} planes in the adsorption of sensitizing dyes.
0} plane and a method that utilizes the difference in adsorption dependence, for example, T.
It can be determined by the method described in Tani, J. Imaging Sci., 29,165 (1985).

In the present invention, the area ratio (Cub) of the {100} plane can be calculated by the following equation.

Cub = {(W (d) × NA × S (d) × 100) / Mw
(d) × S (g)} [%] where W (d): Saturated adsorption amount of the dye on the non- {111} surface NA: Avogadro's number S (d): Area occupied by one dye molecule Mw ( d): molecular weight of dye S (g): total particle surface area Furthermore, the area ratio of the {100} plane of the edge portion (ECu
b) can be obtained by the following equation.

ECub = Cub × (ECD + 2t) / 2t where ECD: grain size t: grain thickness The area ratio of the {100} plane at the edge is 1
It is preferably 5% or more, more preferably 30%
Or more, More preferably, it is 50% or more.

In the present invention, the appearance location of the {100} plane is the edge portion of the hexagonal flat plate.

In the silver halide emulsion of the present invention, {1
To control the {00} plane ratio, see Japanese Patent Application Laid-Open No. 2-29.
The description such as 8935 can be referred to. More specifically, controls such as silver halide grain growth pAg, silver halide solvent concentration, and silver halide grain growth pH are preferably used. It can also be controlled by the presence of a compound represented by the following general formula [I].

More preferably, the presence of these compounds is controlled or the growth pAg is controlled.

General formula [I] YO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _p (CH ₂ CH ₂ O) _n Y In general formula [I], Y is a hydrogen atom, SO ₃ M or -COBC
Represents OOM. M represents a hydrogen atom, an alkali metal atom, an ammonium group or an alkyl-substituted ammonium group having 5 or less carbon atoms, and B represents a chain or cyclic group forming an organic dibasic acid. m and n each represent an integer of 0 to 50, and p represents an integer of 1 to 100. Hereinafter, the general formula [I]
Representative specific examples of the described compounds are shown.

[0034]

Embedded image

In the present invention, the addition amount of these compounds is preferably 5 × 10 ^-2 g to 10 g per mol of silver.

In the present invention, the silver iodide content and the average silver iodide content of individual silver halide grains are determined by the EPMA method (Ele
It can be obtained by using the ctron Probe Micro Analyzer method). According to this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared, and elemental analysis of an extremely minute portion can be performed as compared with X-ray analysis by electron beam excitation of electron beam irradiation.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensity of silver and iodide emitted from each grain. When the silver iodide content of at least 50 grains is determined by the EPMA method, the average silver iodide content can be determined from the average thereof.

In X-ray photoelectron spectroscopy, prior to its measurement, the emulsion is pretreated as follows. First, the emulsion is about 1m
10 ml of 0.01 wt% aqueous solution of pronase was added to
Gelatin is decomposed by stirring at 40 ° C. for 1 hour. Next, the emulsion particles are settled by centrifugation, the supernatant is removed, 10 ml of a pronase aqueous solution is added, and gelatin is decomposed again under the above conditions. Centrifuge the sample again,
After removing the supernatant, 10 ml of distilled water is added to redisperse the emulsion particles in distilled water, and the mixture is centrifuged to remove the supernatant. After repeating this washing operation three times, the emulsion grains are redispersed in ethanol (the work up to this point is performed in a dark room). This is thinly coated on a mirror-polished silicon wafer in a dimly lit room to obtain a measurement sample. The sample coated on the silicon wafer is measured by X-ray photoelectron spectroscopy within 24 hours.

For measurement by X-ray photoelectron spectroscopy, an ESCA / SAM560 type manufactured by PHI is used as an apparatus.
The sample is fixed to a 60-degree tilt holder, and the sample pre-evacuation chamber is evacuated for 10 minutes using a turbo molecular pump, and then introduced into the measurement chamber. Irradiation of excitation X-rays (Mg-Kα rays) is started within 1 minute after introduction of the sample, and measurement is started immediately.

The measurement is carried out under the conditions of an X-ray source voltage of 15 kV, an X-ray source current of 40 mA and a pass energy of 50 eV.

Ag 3 was used to determine the surface halide composition.
d, Br 3d, I 3d 3/2 electrons are detected. Ag
To detect 3d electrons, the binding energy from 381 eV to 36
The range of 1 eV is measured once for each scan step 0.2 eV and each step 100 msec. For the detection of Br 3d electrons, the range of total energy 79 eV to 59 eV is scan step 0.2 eV, each step 100 msec.
5 times each, and for the detection of I3d3 / 2 electrons, a total energy range of 644 eV to 624 eV is measured by scanning step 0.2 eV and each step 100 msec 40 times. The data is obtained by repeating the above operation twice.

The integrated intensity of each peak is used to calculate the composition ratio. The integrated intensity of the Ag 3d peak is the intensity of the energy value obtained by adding 4 eV to the total energy at which the Ag 3d 3/2 peak shows the maximum value, and the intensity of the energy value obtained by adding 4 eV to the binding energy at which the Ag 3d 5/2 peak shows the maximum value. The straight line connecting the lines is taken as the base line, and the integrated intensity of the Br 3d peak is calculated as cps · eV.
Unit of cps · eV with a straight line connecting the intensity of the energy value obtained by adding 4eV to the total energy at which the peak has the maximum value and the intensity of the energy value obtained by subtracting 3eV from the total energy at which the peak of Br 3d5 / 2 has the maximum value. And the integrated intensity of the I 3d 3/2 peak is I 3d
A straight line connecting the intensity of the energy value obtained by adding 4 eV to the total energy at which the 3/2 peak has the maximum value and the intensity of the energy value obtained by subtracting 4 eV from the total energy at which the I 3d 3/2 peak has the maximum value is cps. Obtained in units of eV. When the composition ratio is calculated from the integrated intensity of each peak, the relative sensitivity coefficient method is used and Ag 3
By using 5.10, 0.81, and 4.592 as the relative divisors of d, Br 3d, and I 3d 3/2, respectively, the composition ratio is given in atomic percent.
I mole percent is determined by dividing the atomic percent value of I by the atomic percent value of Br and the atomic percent value of I.

The emulsion of the present invention preferably has a more uniform iodine content between grains.

The silver halide grains according to the present invention preferably have a more uniform iodide content between grains.
When the distribution of the iodide content between grains is measured by the EPMA method, the relative standard deviation is preferably 35% or less, more preferably 20% or less.

The average silver iodide content of the emulsion of the present invention is preferably 2 to 12 mol%.

The dislocations of the silver halide grains relating to the present invention are described, for example, in JF Hamilton, Phot.Sci.Eng., Vol11,57.
(1967), T. Shiozawa, J.Soc.Phot.Sci.Japan, vol35,21
3 (1972) and can be observed by a direct method using a transmission electron microscope at low temperature. That is,
Carefully remove the silver halide grains from the emulsion so that dislocations do not occur in the grains, place them on a mesh for electron microscope observation, and cool the sample to prevent damage (printout, etc.) due to electron beams. Observe by the transmission method in the state. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). .

From the photograph of the grains obtained by such a method, the position and the number of dislocations of each grain when viewed from the direction perpendicular to the principal plane can be determined.

In the emulsion of the present invention, the proportion occupied by tabular silver halide grains having 10 or more dislocation lines in each grain fringe portion is 50% or more, preferably 7 or less.
It is 0% or more, more preferably 90% or more, and further preferably 95% or more.

The grain fringe portion in the present invention means the outer periphery of the tabular grain. Specifically, it is preferable that dislocation lines are generated in the region of 0.6 L to L from the center of the silver halide grain toward the outer surface, and more preferably 0.7
0L to L, and more preferably 0.80L to L.

The direction of the dislocation lines is approximately the direction from the center to the outer surface, but it often meanders.

In the present invention, the center of silver halide means
The silver halide microcrystals were dispersed in methacrylic resin and solidified, and ultrathin sections were obtained with a microtome. Focusing on the section sample having the maximum cross-sectional area or a cross-sectional area of 90% or more, Is the center of the circle when the smallest circumscribed circle is drawn.

In the present invention, the distance L from the center to the outer surface is defined as the distance between the center of the circle and the point intersecting the outer circumference of the particle when a straight line is drawn from the center of the circle to the outside.

Introduction of dislocation lines into the silver halide according to the present invention can be achieved by providing a high silver iodide layer at a specific site inside the grain. Here, the high silver iodide layer includes a case where the high silver iodide layer is discontinuously provided. Specifically, it can be obtained by preparing a base grain and then providing a high silver iodide layer and covering the outside thereof with a layer having a lower silver iodide content than the high silver iodide layer. The silver iodide content of the base silver halide grains is lower than that of the high silver iodide layer, preferably 0 to 20 mol%, more preferably 0 to 15 mol%.

The high silver iodide layer inside the grain is preferably silver iodide, silver iodobromide or silver chloroiodobromide as the silver halide containing silver iodide, but silver iodide or silver iodobromide ( The silver iodide content is preferably 5 to 40 mol%). The so-called conversion (halogen substitution) method can be used to form the internal high-iodity layer. This method includes, for example, a method of adding a halogen ion having a lower solubility of a salt forming a silver ion than a halogen ion forming the particle or the surface of the particle at that time during the formation of the particle.

A more preferable method of forming an internal high-iodine silver layer is to add Ag at the same time as the addition of an aqueous halide salt solution containing an iodide salt.
The NO ₃ aqueous solution is added with a double jet. KI at this time
The addition start time and the addition end time of the aqueous solution and the AgNO ₃ aqueous solution may be shifted back and forth. Most preferably, the formation of the internal high silver iodide layer is carried out by adding fine grain silver iodide (fine grain silver iodide), fine grain silver iodobromide, fine grain silver chloroiodide or fine grain silver chloroiodobromide. You can It is particularly preferable to add fine grain silver iodide. These fine particles usually have a particle size of 0.01 μm or more and 0.1 μm or less, but fine particles having a particle size of 0.01 μm or less or 0.1 μm or more can also be used. An internal high silver iodide layer can be provided by adding and ripening these fine grain silver halides. It is not necessary for all of the added fine particles to be dissolved and disappeared immediately, as long as they are dissolved and disappeared when the final particles are completed.

The silver iodide content of the outer layer covering the internal high silver iodide layer is lower than that of the internal high silver iodide layer, preferably 0 to 30 mol%, more preferably 0. ~ 20
Mol% More preferably 0 to 10 mol%.

When introducing dislocations according to the present invention, the amount of iodide ion required to form a high silver iodide layer at a specific site inside the grain is 0.01 to 10 mol% with respect to the host grain.
Is preferable, and more preferably 0.5 to 5 mol%.

The silver halide grains according to the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method, and the method of reacting a soluble silver salt with a soluble silver halide is a side mixture. Any of a method, a simultaneous mixing method, and a combination thereof may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of the simultaneous mixing method, a method of keeping pAg constant in a liquid layer in which silver halide is produced, that is, a so-called controlled double jet method can be used.

Further, two or more kinds of silver halides formed separately may be mixed and used.

The silver halide grains according to the present invention are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), indium salt and rhodium during the grain forming process and / or growing process. A metal ion may be added using at least one selected from a salt (including a complex salt) and an iron salt (including a complex salt), and these metal elements may be contained inside and / or on the surface of the particle. A reduction sensitizing nucleus can be imparted to the inside of the grain and / or the surface of the grain by placing in a different reducing atmosphere.

As a method for obtaining a monodisperse emulsion, two or more kinds of reactions arbitrarily selected from a water-soluble silver salt solution, a water-soluble halide solution, and silver halide fine particles are added to a gelatin solution containing seed particles. Elements can be obtained by adding under controlled pAg and pH. In determining the addition rate, JP-A-54-48521 and JP-A-SHO-5
Reference can be made to No. 8-49938.

As a method for obtaining a more advanced monodisperse emulsion, the growth method in the presence of tetrazaindene disclosed in JP-A-60-122935 can be applied.

A known silver halide solvent such as ammonia, thioether or thiourea may be present during the production of the silver halide grains according to the present invention, or the silver halide solvent may not be used.

The silver halide grains according to the present invention are produced in the presence of a dispersion medium, that is, in a solution containing the dispersion medium.

Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed by a substance that can form a hydrophilic colloid such as gelatin (a substance that can be a binder), and is preferably a colloid. An aqueous solution containing a protective gelatinous form.

When gelatin is used as the protective colloid in carrying out the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964).

Hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-
There are various types of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers.

In the case of gelatin, it is preferable to use one having a jelly strength of 200 or more in the Paggy method.

The silver halide grains according to the present invention may be those in which unnecessary soluble salts have been removed after the growth of the silver halide grains has been completed, or the grains may be contained as they are.

Further, as in the method described in JP-A-60-138538, desalting can be carried out at any point of silver halide growth. The removal of the salts can be carried out according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II. More specifically, in order to remove the soluble salt from the emulsion after the precipitation or after the physical ripening, a Nudel water washing method performed by gelatinizing gelatin may be used, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (for example, polystyrenesulfonic acid) or a gelatin derivative (for example, acylated gelatin, carbamoylated gelatin, etc.) may be used.

The silver halide grains according to the present invention can be chemically sensitized by a conventional method. That is, a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method using a gold or other noble metal compound can be used alone or in combination.

The silver halide grain according to the present invention can be optically sensitized in a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more kinds. A dye that does not have a spectral sensitizing effect by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing effect of the sensitizing dye is included in the emulsion. May be.

Antifoggants, stabilizers and the like can be added to the silver halide grains according to the present invention. It is advantageous to use gelatin as the binder. The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or soluble synthetic polymer.

A coupler is used in the emulsion layer of the color light-sensitive material. Furthermore, a development accelerator, a developer, a silver halide solvent, a toning agent, a hardener, by coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent,
Compounds that release photographically useful fragments such as fog agents, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an antiirradiation layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during the development processing may be contained. Matting agents, lubricants, image stabilizers, formalin scavengers, ultraviolet absorbers, optical brighteners, surfactants, development accelerators and development retarders can be added to the light-sensitive material.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

[0078]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited thereto.

Example 1 Preparation of Twin Crystal Emulsion T-1 A seed emulsion having two parallel twin planes was prepared by the following method.

Liquid A Ossein gelatin 80.0 g Potassium bromide 47.4 g HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10% by weight methanol solution 0.48 ml Finish with distilled water to 8000.0 ml Solution B Silver nitrate 1200.0 g Finish with distilled water to 1600.0 ml Solution C Ossein gelatin 32.2 g Potassium bromide 823.8 g Potassium iodide 23.45 g Finish with distilled water to 1600.0 ml Solution D Ammonia water 470.0 ml Solution A and solution C which were vigorously stirred at 40 ° C. were added with solution B and solution C by the double jet method in 7.7 minutes to generate nuclei. During this period, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Furthermore, the D liquid was added in 1 minute, and the aging was continued for 5 minutes. KBr concentration during aging is 0.03m
The ol / l and the ammonia concentration were 0.66 mol / l.

After completion of aging, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. A 10% by weight aqueous gelatin solution was added to the desalted emulsion, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and distilled water was added to the emulsion to give an emulsion of 5360 g.

When the seed emulsion grains were observed with an electron microscope, they were tabular grains having two parallel twin planes.

The average grain size of the seed emulsion grains is 0.295 μm.
The number of particles having m, an average aspect ratio of 5.0, and two parallel twin planes was 80% (the number ratio) of all particles.

Preparation of Comparative Emulsion EM-1 A comparative emulsion EM-1 was prepared using the following 7 kinds of solutions.

Solution A Ossein gelatin 67.0 g Distilled water 3176.0 ml HO (CH ₂ CH ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) 10 Weight% Methanol solution 2.50 ml Seed emulsion (T-1) 98.51 g Finish to 3500 ml with distilled water Solution B 3.5N Silver nitrate aqueous solution 4606 ml Solution C potassium bromide 1915.1 g Ocein gelatin 200 g Finish to 4606 ml with distilled water Solution D 3 Fine grain emulsion (*) consisting of gelatin in weight% and silver iodide grains (average grain size 0.05 μm) 2465.5 g The method for preparing the fine grain emulsion (*) is shown below. A 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide 5
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added to 10 ml of 000 ml.
Added over minutes. The pH during fine particle formation was controlled to 2.0 using nitric acid, and the temperature was controlled to 40 ° C. After particle formation,
The pH was adjusted to 6.0 with aqueous sodium carbonate solution. The finished weight was 12.53 kg.

Solution E 1.75N aqueous solution of potassium bromide Solution A was added to a reaction vessel and stirred vigorously to prepare solution B-
Solution D was added by the simultaneous mixing method to grow a seed crystal to prepare a core / shell type silver halide emulsion. Up to 65% of the total amount of silver added, solution C and solution D were added so that the molar ratio was 9: 1, and after 65%, only solution B and solution C were added.

Here, the addition rates of (1) solution B, solution C and solution D, and (2) solution B and solution C were set so as to correspond to the critical growth rate of silver halide grains. However, the addition rate was controlled so as to prevent polydispersion due to generation of small particles and Ostwald ripening other than growing seed crystals.

Further, the temperature of the solution in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 9.0 over the entire area of the crystal growth. Solution E was added as needed for pAg control.

Thereafter, desalting treatment was performed according to the method described in JP-A-5-72658, gelatin was added, and the temperature was 50 ° C.
Re-disperse for 30 minutes, cool to 40 ° C and adjust pH to 5.8
0, pAg was adjusted to 8.06. From an electron micrograph of the obtained emulsion grains, it was confirmed that the grains were tabular grains having an average grain size of 1.99 μm, an average aspect ratio of 8.5 and a grain size distribution of 18.0%.

Preparation of Comparative Emulsion EM-2 In the production method of Emulsion EM-1, 65% of the total amount of added silver was used.
At the end of step 1, the addition of solutions B to D was stopped, and solution D corresponding to 2 mol% of the total amount of silver added was added over 2 minutes.
A comparative emulsion EM-2 was prepared by the same production method as for the emulsion EM-1, except that the ripening was carried out for 0 minutes.

Preparation of Emulsion EM-3 of the Present Invention In the production method of Emulsion EM-2, 85% of the total amount of added silver was used.
PAg was lowered to 8.0 at the end of the above step, and the emulsion EM- of the present invention was produced by the same production method as for the emulsion EM-2 except for the above.
3 was prepared.

Preparation of Emulsions EM-4 and EM-5 for the Present Invention In the production method of Emulsion EM-3, 65% of the total amount of added silver was used.
Emulsions EM-4 and EM-5 of the present invention were prepared by the same production method as for the emulsion EM-3 except that the pAg until the end of was raised to 9.0 or higher.

Preparation of Comparative Emulsion EM-6 In the production method of Emulsion EM-3, 65% of the total amount of added silver was used.
Comparative Emulsion EM-6 was prepared in the same manner as Emulsion EM-3, except that the pAg until the end of the step was changed to 8.4.
Was prepared.

Preparation of Comparative Emulsion EM-7 In the production method of Emulsion EM-1, 65% of the total amount of added silver was used.
Comparative Emulsion EM-6 was prepared in the same manner as Emulsion EM-3, except that the pAg until the end of the step was changed to 8.4.
Was prepared.

Table 1 shows the characteristics of the emulsions EM-1 to EM-7.

[0097]

[Table 1]

As can be seen from Table 1, in the emulsion in which silver iodide fine particles were added during the growth of silver halide grains, generation of dislocation lines was recognized in the fringe portion of the grains. Also, {1
The {00} plane ratio usually decreases as the aspect ratio increases, but by lowering the pAg of the shell, the {100} plane appears at the edge portion and the {100} plane ratio also rises. I understand.

Example 2 (Preparation of Photosensitive Material Sample) EM-1 to EM-7 were subjected to gold-sulfur sensitization, and these emulsions were used to prepare a composition as shown below on a triacetyl cellulose film support. Each layer was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material.

In all the following descriptions, the addition amount in the silver halide photographic light-sensitive material is 1 m unless otherwise specified.
^The number of grams per ² is shown. Further, silver halide and colloidal silver are shown in terms of silver, and sensitizing dyes are shown in the number of moles per mole of silver halide.

The constitution of the multilayer color photographic light-sensitive material sample-1 (using the comparative emulsion EM-1) is as follows.

Multilayer color photographic light-sensitive material Sample-1 First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound ( SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low sensitivity red sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD-2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Middle red sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 Sensitizing dye (SD-2) 0.86 × 10 ^-4 Sensitizing dye (SD-3) 1.15 × 10 ^-5 Sensitizing dye (SD-4) 0.86 × 10 ^-4 Cyan coupler (C-1) 0 .33 Colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 High boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Fifth layer: high sensitivity red sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye ( SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) ) 0.016 High boiling point solvent (OIL-1) 0.16 Gelatin
0.79 Layer 6: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Layer 7: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitized Dye (SD-4) 4.6 × 10 ^-5 Sensitizing Dye (SD-5) 4.1 × 10 ^-4 Magenta Coupler (M-1) 0.14 Magenta Coupler (M-2) 0.14 Colored Magenta Coupler (CM-1) 0.06 High Boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium sensitivity green sensitive layer Emulsion EM-1 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 ^-4 Sensitizing dye (SD-7) 1.2 × 10 ^-4 Sensitizing dye (SD-8) 1.2 × 10 ^-4 Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM- 1) 0.017 DIR compound (D-2) 0.025 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 Layer 10: high sensitivity green sensitive layer Iodobromide Emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 -5 Sensitizing dye (SD-7) 7.1 × 10 -5 Sensitizing dye (SD-8) 7.1 × 10 -5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 No. 12 layers: low-sensitivity blue-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 No. 13 layer: high sensitivity blue-sensitive layer silver iodobromide emulsion C 0.15 silver iodobromide emulsion E 0.80 sensitizing dye (SD-9) 8.0 × 10 -5 sensitizing dye (SD-11) 3.1 × 10 - ⁵ Ye -Coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorption Agent (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High boiling point solvent (OIL-3) 0.07 Gelatin 0.65 15th layer: 2nd protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmethacrylate ( Average particle size 3 μm) 0.04 Sliding agent (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two types of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

The emulsions used in the above samples are shown in Table 2 below. The average particle size is shown as a particle size converted into a cube. Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0104]

[Table 2]

The structural formulas of the compounds used for the production of the above light-sensitive material are shown below.

[0106]

Embedded image

[0107]

Embedded image

[0108]

[Chemical 4]

[0109]

Embedded image

[0110]

[Chemical 6]

[0111]

[Chemical 7]

[0112]

Embedded image

[0113]

[Chemical 9]

[0114]

[Chemical 10]

[0115]

[Chemical 11]

[0116]

[Chemical 12]

The emulsions EM-2 to EM-7 are also shown in Table 3.
As shown in (1), by using each of these emulsions in place of the emulsion EM-1 of Sample-1, multilayer color photographic light-sensitive material samples-2 to 7 were similarly prepared.

[0118]

[Table 3]

After subjecting each of the samples prepared as described above to wedge exposure using green light (G),
The development processing shown below was performed, and the relative sensitivity, graininess, and pressure resistance were measured.

Treatment process 1. Color development 3 minutes 15 seconds 38.0 ± 0.1 ° C 2. Bleach 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Water washing 3 minutes 15 seconds 24-41 ° C 4. Fixation 6 minutes 30 seconds 38.0 ± 3.0 ℃ 5. Washing with water 3 minutes 15 seconds 24 to 41 ℃ 6. Stability 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying 50 ℃ or less The composition of the processing solution used in each processing step is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter and pH is adjusted to 10.1.

<Bleach> Ethylenediaminetetraacetic acid ammonium ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using ammonia water. .

<Fixer> Ammonium thiosulfate 175.0 g anhydrous sodium sulfite 8.5 g sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (Konica Corp.) 7.5 ml Water is added to make 1 liter.

The results obtained are shown in Table 4.

[0126]

[Table 4]

In Table 4, the relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of Dmin (minimum density) +0.1, and the sensitivity of Sample-1 immediately after preparation of the sample is 100. (For 100, the larger the value, the higher the sensitivity).

Regarding the pressure resistance, a scratch strength tester (manufactured by Shinto Kagaku) was used under the conditions of 23 ° C. and 55% (relative humidity), and a load of 5 g was applied to a needle having a radius of curvature of 0.025 mm at the tip. After scanning at a constant speed by applying, exposure, development processing is performed,
For the pressure fog, the density change (ΔDp1) of the portion under load at the density of Dmin was obtained,
ΔDp1 of 100 is shown as a value (the smaller the value is, the better the improvement is). For pressure desensitization, the density change (ΔDp2) in the portion where a load is applied at the density of Dmin + 0.1 was obtained, and the sample-
The value is shown with the value of ΔDp2 of 1 being 100 (the smaller the value with respect to 100, the better the improvement).

The RMS value is obtained by scanning the density of the measured portion of the sample with a microdensitometer having an opening scanning area of 1800 μm 2 (slit width 10 μm, slit length 180 μm), and measuring the concentration standard of fluctuation of density value of 1000 or more. It is shown as a relative value with 1000 times the deviation value as 100.

As is clear from the results shown in Table 4, the sample of the present invention containing the emulsions EM-3,4,5 according to the present invention-
3, 4, 5 have high sensitivity, improved graininess, and pressure resistance
(Pressure fog, pressure desensitization) has been improved. Among these, the emulsion EM which satisfies the best combination of the present invention.
Sample-5 using -5 is particularly excellent.

As described above, according to the invention of the present application, a silver halide photographic light-sensitive material excellent in sensitivity, graininess and pressure resistance can be obtained.

[0132]

According to the present invention, a silver halide photographic emulsion and a silver halide color photographic light-sensitive material having high sensitivity, improved graininess, and improved pressure resistance are provided.

Claims (2)

[Claims] 1. A silver halide photographic emulsion containing silver halide grains in a dispersion medium, wherein the grain size distribution of the silver halide grains is monodisperse, and the total projected area of the silver halide grains is 50%. The silver halide grains occupying the above have an aspect ratio of 8 or more and mainly {111} and {100}
A tabular silver halide grain comprising a surface and a grain fringe portion having 10 or more dislocation lines per grain, the silver halide photographic emulsion. 2. A silver halide color photographic light-sensitive material having at least one silver halide emulsion on a support, wherein at least one silver halide emulsion layer is formed.
A silver halide color photographic light-sensitive material comprising the described silver halide photographic emulsion.